CN111020549A - Chromium-free passivation solution for zinc-aluminum-magnesium coating plate - Google Patents
Chromium-free passivation solution for zinc-aluminum-magnesium coating plate Download PDFInfo
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- CN111020549A CN111020549A CN201911391337.9A CN201911391337A CN111020549A CN 111020549 A CN111020549 A CN 111020549A CN 201911391337 A CN201911391337 A CN 201911391337A CN 111020549 A CN111020549 A CN 111020549A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/368—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing magnesium cations
Abstract
The invention provides a chromium-free passivation solution for a zinc-aluminum-magnesium plating plate, which comprises an aqueous medium and at least the following components in a dissolved/dispersed state in the aqueous medium: aluminum ions, phosphate, fluoric acid, oxidant and resin. According to the invention, through the combination of an oxidant, phosphate and fluoric acid, aluminum ions are introduced as film forming ions, and through the synergistic effect of the phosphorization and the oxidation processes, the corrosion resistance and the water resistance of the zinc-magnesium-aluminum coating are improved, the blackening tendency of magnesium-aluminum metal is effectively inhibited, and the adhesive force of the coating is greatly improved through the introduction of resin. Because unstable components such as silane and the like are not used, the stability of the passivation solution can be improved to more than one year. And the main components of the composition are inorganic components, so that the protective effect on magnesium aluminum metal or a plating layer can be realized under the condition of a film layer, and the drying condition is only 50-60 ℃, so that the use cost of chromium-free passivation is greatly reduced, and the application range of the magnesium aluminum metal or the alloy plating layer is expanded.
Description
Technical Field
The invention relates to a passivation solution for surface treatment and corrosion prevention of metal materials, in particular to a chromium-free passivation solution for a zinc-aluminum-magnesium plating plate.
Background
(1) The zinc-aluminum-magnesium alloy is an alloy metal and mainly used for surface anticorrosion treatment of steel and steel products, and comprises various zinc series coatings and a large amount of steel products for integral immersion plating corrosion prevention; the metal used for the surface anticorrosion treatment of steel products at first is pure zinc, and with the improvement of the technology, alloy metals such as aluminum-zinc alloy, zinc-aluminum-magnesium alloy and the like appear in succession, so that the corrosion resistance effect of the metal layer is improved.
Originally developed and mass-produced in the 21 st century by the japanese new-day steel company in japan, the purpose of which was to replace some application scenarios of stainless steel. At present, wine steel, Tang steel and Bao steel are all produced in domestic steel mills, and the material is gradually widely applied along with the industrial upgrading in the later period.
The zinc-aluminum-magnesium coated steel sheet is a coated steel sheet which is added with a certain amount of Al and Mg in the existing hot galvanizing coating or added with a certain amount of Mg element in the hot galvanizing aluminum-zinc coating, and has the characteristics of high corrosion resistance and high edge cutting protection performance. The zinc-aluminum-magnesium coating is an alloy metal with very excellent comprehensive performance, the manufacturing cost is only slightly higher than that of an aluminum-zinc coating, the corrosion resistance of the coating is far higher than that of pure zinc and aluminum-zinc alloy, the protection performance on the steel plate cuts is very good, and the welding performance is equivalent to that of a pure zinc steel plate. The zinc-aluminum-magnesium steel plate in the market has direct application cases, and meanwhile, the zinc-aluminum-magnesium color-coated plate applied as a color substrate is also applied in a large amount by realizing mass production, the direct naked zinc-aluminum-magnesium steel plate belongs to high-aluminum zinc-aluminum magnesium, and the zinc-aluminum-magnesium steel plate used as the color substrate belongs to low-aluminum zinc-aluminum magnesium. With the increasing requirements of buildings and various industries on materials in the future, the zinc-aluminum-magnesium coated steel plate can possibly gradually replace the application of aluminum-zinc coated steel plates in the market.
(2) The current conventional chromium-free passivation is divided into two categories, one being a weakly acidic system based on hydrolyzed silanes, such as:
1) the invention discloses a chromium-free passivation solution for the surface of a galvanized layer, which is published (announced) by No. CN102337532A application (patent) of Wuhandisi high-tech research and development Co., Ltd;
2) the invention relates to a chromium-free passivation solution and a hot-dip galvanized metal material, which is published by CN102373453A application (patent right) Pan Steel group vanadium titanium company Limited;
3) title of the invention-composition for surface treatment of metallic material and treatment method, public disclosure (bulletin) No. -CN1814860A application (patent right) entitled trademarks of rice-flour-paste corps;
the common characteristics of the systems are that one or more silane hydrolysates are used as main film forming substances, the PH is 4-6, and the base material is mainly galvanized.
Another is a weakly basic system based on resins, for example:
U.S. Pat. No. 5, 00,52226, Assignee, Henkel corporation, Gulph mills, Pa. The common characteristics of the systems are that one or more resins are adopted as main film forming substances, the PH is 8-10, and the base material is mainly plated with aluminum and zinc.
Due to the strong activity of the galvanized aluminum magnesium plate, the original product system cannot meet the requirements of new base materials, such as:
the silane formula is very easy to generate a blackening phenomenon in a damp-heat test, a zinc-aluminum-magnesium plate has a very strong blackening tendency, uneven black spots and the phenomenon of blackening of the whole plate are very easy to generate under the condition that a passivation film is not coated, the blackening tendency cannot be changed after the silane formula is coated with a passivation solution of a silane system, and particularly, the plate surface is seriously blackened after being stored for a long time, so that the requirements of downstream customers cannot be met.
The protection of the resin formulation against the zn-al-mg panels is usually insufficient, and the salt spray test is short, usually less than 120 hours or even 72 hours, and it is difficult to meet the requirements of downstream customers for corrosion resistance. Meanwhile, the resin formula also has the problem of blackening of the board surface after long-term storage.
The proposal aims to introduce new chemicals into the existing production line, protect the zinc-aluminum-magnesium substrate from white rust and black spots during transportation and storage, and provide a qualified passivated plate.
Therefore, the invention is produced.
Disclosure of Invention
In view of the above, the present invention provides a passivation solution applicable to a zinc-aluminum-magnesium plating plate to overcome the blackening phenomenon when a silane-formulated passivation solution is applied to a zinc-aluminum-magnesium plating plate and the disadvantage of poor salt spray resistance when a resin-formulated passivation solution is applied to a zinc-aluminum-magnesium plating plate, and the invention provides a chromium-free passivation solution for a zinc-aluminum-magnesium plating plate, which is characterized by comprising an aqueous medium and at least the following components present in the aqueous medium in a dissolved/dispersed state: aluminum ions, phosphate, fluoric acid, oxidant and resin.
The invention has the beneficial effects that:
according to the invention, through the combination of an oxidant, phosphate and fluoric acid, aluminum ions are introduced as film forming ions, and through the synergistic effect of the phosphorization and the oxidation processes, the corrosion resistance and the water resistance of the zinc-magnesium-aluminum coating are improved, the blackening tendency of magnesium-aluminum metal is effectively inhibited, and the adhesive force of the coating is greatly improved through the introduction of resin. Because unstable components such as silane and the like are not used, the stability of the passivation solution can be improved to more than one year. And the main components of the composition are inorganic components, so that the protective effect on magnesium aluminum metal or a plating layer can be realized under the condition of a film layer, and the drying condition is only 50-60 ℃, so that the use cost of chromium-free passivation is greatly reduced, and the application range of the magnesium aluminum metal or the alloy plating layer is expanded.
Preferably, the aluminum ions and the phosphate are aluminum-containing phosphate or organic phosphonate, and are selected from one or more of the following components in combination: aluminum tripolyphosphate, aluminum dihydrogen phosphate, PA80 glue, and organic aluminum hypophosphite.
Preferably, the aluminium-containing phosphate or organophosphonate represents from 5% to 45% of the total components present in dissolved/dispersed state in the aqueous medium.
Preferably, the fluoric acid is transition metal fluoric acid selected from one or more of the following components in combination: fluozirconic acid, fluotitanic acid and fluohafnic acid.
Preferably, the transition metal fluoroacid is present in the aqueous medium in a dissolved/dispersed state in an amount of 0.5% to 5.5% of the total composition.
Preferably, the oxidant is an oxidizing salt selected from one or more of the following components in combination: zinc nitrate, manganese nitrate, cerium nitrate, aluminum nitrate, nickel nitrate, copper nitrate, iron nitrate, magnesium nitrate, zirconyl nitrate, zirconium nitrate, titanium nitrate.
Preferably, the oxidizing salt accounts for 3 to 30% of the total components present in the aqueous medium in dissolved/dispersed state.
Preferably, the resin is selected from one or more of the following components in combination: cationic or nonionic resins, such as acrylic resin, polyurethane resin, and epoxy resin.
Preferably, the resin accounts for 20 to 80% of the total components present in the aqueous medium in a dissolved/dispersed state.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Comparative example 1: hydrolytic aminosilane and epoxy silane are used as main bodies, the pH value is 4-6, other components are transition metal fluoroacid, phosphoric acid, acrylic resin and the like, the corrosion resistance, the wet heat resistance and the recoatability are good on a galvanized substrate, the wet heat resistance and the recoatability are extremely poor on a zinc-aluminum-magnesium substrate, the surface color difference Delta E is more than or equal to 5 after a 120-hour wet heat experiment (49 ℃ and 98 percent relative humidity), and the customer requirements cannot be met.
Comparative example 2: the resin content is 55%, the PH is 8-9, other components comprise zirconium salt and phosphate, better corrosion resistance and damp-heat property can be provided on a galvanized substrate, but the salt fog performance on a zinc-aluminum-magnesium substrate is poor, the corrosion area in a 72-hour salt fog test is more than 10%, and the requirements of customers cannot be met.
In the following examples, components other than water, such as aluminum ions, phosphate, fluoric acid, oxidizing agent, and resin, which are present in an aqueous medium in a dissolved/dispersed state, are referred to as total components.
Example 1: 2% of aluminum dihydrogen phosphate, 4% of zinc nitrate, 24% of aqueous acrylic resin and 0.2% of fluoro hafnate; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounted for 6.62% of the total composition, zinc nitrate accounted for 13.25% of the total composition, aqueous acrylic resin accounted for 79.47% of the total composition, and hafnium fluoride acid accounted for 0.66% of the total composition.
Example 2: 10% of aluminum dihydrogen phosphate, 6% of zinc nitrate, 12% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounts for 33.9% of the total composition, zinc nitrate accounts for 20.34% of the total composition, the aqueous acrylic resin accounts for 40.68% of the total composition, and fluotitanic acid accounts for 5.08% of the total composition.
Example 3: 8% of aluminum dihydrogen phosphate, 6% of zinc nitrate, 15% of water-based epoxy resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounts for 26.23% of the total composition, zinc nitrate accounts for 19.67% of the total composition, aqueous epoxy resin accounts for 49.18% of the total composition, and fluotitanic acid accounts for 4.92% of the total composition.
Example 4: 8% of aluminum dihydrogen phosphate, 6% of magnesium nitrate, 12% of aqueous polyurethane resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounted for 29.09% of the total composition, magnesium nitrate accounted for 21.82% of the total composition, aqueous urethane resin accounted for 43.64% of the total composition, and fluotitanic acid accounted for 5.45% of the total composition.
Example 5: 10% of organic aluminum phosphate, 1% of cerium nitrate, 18% of waterborne polyurethane resin and 1% of fluorozirconic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, the aluminum organophosphate accounts for 33.33% of the total composition, the cerium nitrate accounts for 3.33% of the total composition, the aqueous polyurethane resin accounts for 60% of the total composition, and the fluorozirconic acid accounts for 3.33% of the total composition. It is worth mentioning that the error in the actual feeding is 0.01%, but the actual product effect is not influenced.
Example 6: 8% of aluminum dihydrogen phosphate, 6% of aluminum nitrate, 15% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounted for 26.23% of the total composition, aluminum nitrate accounted for 19.67% of the total composition, aqueous acrylic resin accounted for 49.18% of the total composition, and fluotitanic acid accounted for 4.92% of the total composition.
Example 7: PA 8010%, zinc nitrate 6%, water-based acrylic resin 13%, and fluozirconic acid 1.5%; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, PA80 accounted for 32.79% of the total composition, zinc nitrate accounted for 19.67% of the total composition, aqueous acrylic resin accounted for 42.63% of the total composition, and fluorozirconic acid accounted for 4.92% of the total composition. It is worth mentioning that the error in the actual feeding is 0.01%, but the actual product effect is not influenced.
Example 8: 10% of aluminum dihydrogen phosphate, 3% of manganese nitrate, 17% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounts for 31.75% of the total composition, manganese nitrate accounts for 9.52% of the total composition, aqueous acrylic resin accounts for 53.97% of the total composition, and fluotitanic acid accounts for 4.76% of the total composition.
Example 9: 10% of organic aluminum phosphate, 2% of zirconium nitrate, 16% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, the aluminum organophosphate accounted for 33.90% of the total composition, the zirconium nitrate accounted for 6.78% of the total composition, the aqueous acrylic resin accounted for 54.24% of the total composition, and the fluorotitanic acid accounted for 5.08% of the total composition.
Example 10: 10% of organic aluminum phosphate, 2% of zirconyl nitrate, 16% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, the aluminum organophosphate accounted for 33.90% of the total composition, the zirconyl nitrate accounted for 6.78% of the total composition, the aqueous acrylic resin accounted for 54.24% of the total composition, and the fluorotitanic acid accounted for 5.08% of the total composition.
Example 11: 10% of organic aluminum phosphate, 2% of ferric nitrate, 16% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, 33.90% of the total content of the organic aluminum phosphate, 6.78% of the total content of the ferric nitrate, 54.24% of the total content of the aqueous acrylic resin, and 5.08% of the total content of the fluotitanic acid.
Example 12: 10% of organic aluminum phosphate, 2% of copper nitrate, 16% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, 33.90% of the total content of the organic aluminum phosphate, 6.78% of the total content of the copper nitrate, 54.24% of the total content of the aqueous acrylic resin, and 5.08% of the total content of the fluotitanic acid.
Example 13: 10% of organic aluminum phosphate, 6% of nickel nitrate, 12% of water-based acrylic resin and 1.5% of fluotitanic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, the aluminum organophosphate accounted for 33.90% of the total composition, the nickel nitrate accounted for 20.34% of the total composition, the aqueous acrylic resin accounted for 40.68% of the total composition, and the fluotitanic acid accounted for 5.08% of the total composition.
Example 14: 10% of organic aluminum phosphate, 1% of titanium nitrate, 16% of waterborne polyurethane resin and 0.5% of fluozirconic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, the aluminum organophosphate accounts for 36.36% of the total composition, the titanium nitrate accounts for 3.64% of the total composition, the aqueous polyurethane resin accounts for 58.18% of the total composition, and the fluorozirconic acid accounts for 1.82% of the total composition.
Example 15: 13% of aluminum dihydrogen phosphate, 8% of zinc nitrate, 8% of waterborne polyurethane resin and 1.5% of fluozirconic acid; and the balance of water, stirring and emulsifying to form the passivation solution after mixing. Specifically, aluminum dihydrogen phosphate accounts for 47.46% of the total composition, zinc nitrate accounts for 30.51% of the total composition, the aqueous polyurethane resin accounts for 16.95% of the total composition, and the fluorozirconic acid accounts for 5.08% of the total composition.
The aluminum ions, phosphate, fluoroacid, oxidant, and resin of examples 1-15 were combined in the following table for the total component ratios:
the physical and chemical index tests of examples 1 to 15 were carried out, and compared with comparative examples 1 to 2 as follows:
| drying temperature | Storage time | Resistance to blackening | Recoatability | Salt fog resistance | |
| Comparative example 1 | 80 | 3 months old | ≥5 | Good effect | 72 hours |
| Comparative example 2 | 80 | 3 months old | ≤3 | Good effect | 48 hours |
| Example 1 | 60 | 12 months old | ≤3 | Good effect | Not less than 72 hours |
| Example 2 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 3 | 60 | 12 months old | ≤3 | Good effect | Not less than 168 hours |
| Example 4 | 60 | 12 months old | ≤3 | Good effect | Not less than 120 hours |
| Example 5 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 6 | 60 | 12 months old | ≤3 | Good effect | Not less than 168 hours |
| Example 7 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 8 | 60 | 12 pieces ofMoon cake | ≤3 | Good effect | Not less than 96 hours |
| Example 9 | 60 | 12 months old | ≤3 | Good effect | Not less than 168 hours |
| Example 10 | 60 | 12 months old | ≤3 | Good effect | Not less than 168 hours |
| Example 11 | 60 | 12 months old | ≤3 | Good effect | Not less than 120 hours |
| Example 12 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 13 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 14 | 60 | 12 months old | ≤3 | Good effect | Not less than 96 hours |
| Example 15 | 50 | 12 months old | ≤3 | Good effect | Not less than 72 hours |
Many modifications may be made by one of ordinary skill in the art in light of the above teachings. Therefore, it is intended that the invention not be limited to the particular details of the embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (9)
1. A chromium-free passivation solution for a zinc-aluminum-magnesium plated sheet, characterized by comprising an aqueous medium and at least the following components present in the aqueous medium in a dissolved/dispersed state: aluminum ions, phosphate, fluoric acid, oxidant and resin.
2. The chromium-free passivation solution according to claim 1, characterized in that: the aluminum ions and the phosphate are aluminum-containing phosphate or organic phosphonate, and are selected from one or more of the following components in combination: aluminum tripolyphosphate, aluminum dihydrogen phosphate, PA80 glue, and organic aluminum hypophosphite.
3. The chromium-free passivation solution according to claim 2, characterized in that: the aluminium-containing phosphate or organophosphonate represents 5% to 45% of the total components present in dissolved/dispersed state in the aqueous medium.
4. The chromium-free passivation solution according to claim 1, characterized in that: the fluoric acid is transition metal fluoric acid and is selected from one or more of the following components: fluorozirconic acid, fluorotitanic acid, fluorohafnic acid, and the like.
5. The chromium-free passivation solution according to claim 4, characterized in that: the transition metal fluoroacid is present in the aqueous medium in a dissolved/dispersed state in an amount of 0.5% to 5.5% of the total composition.
6. The chromium-free passivation solution according to claim 1, characterized in that: the oxidant is an oxidizing salt selected from one or more of the following components: zinc nitrate, manganese nitrate, cerium nitrate, aluminum nitrate, nickel nitrate, copper nitrate, iron nitrate, magnesium nitrate, zirconyl nitrate, zirconium nitrate, titanium nitrate.
7. The chromium-free passivation solution according to claim 6, characterized in that: the oxidizing salt accounts for 3 to 30% of the total components present in the aqueous medium in a dissolved/dispersed state.
8. The chromium-free passivation solution according to claim 1, characterized in that: the resin is selected from one or more of the following components: cationic or nonionic resins, such as acrylic resin, polyurethane resin, and epoxy resin.
9. The chromium-free passivation solution according to claim 8, characterized in that: the resin accounts for 20 to 80% of the total components present in the aqueous medium in a dissolved/dispersed state.
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